The class of polymers of carbon monoxide and olefin(s) has been known for some time. Brubaker, U.S. Pat. No. 2,495,286, produced such polymers of relatively low carbon monoxide content in the presence of free radical initiators, e.g., peroxy compounds. G.B. 1,081,304 produced compounds of higher carbon monoxide content in the presence of alkylphosphine complexes of palladium salts as catalysts. Nozaki extended the reaction to produce linear alternating polymers in the presence of arylphosphine complexes of palladium moieties and certain inert solvents. See, for example, U.S. Pat. No. 3,694,412.
More recently, the class of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon has become of greater interest in part because of the greater availability of the polymers. The more recent processes for the production of such linear alternating polymers, also known as polyketones or polyketone polymers, are illustrated by a number of published European Patent Applications including 121,965, 181,014, 213,671 and 257,663. The processes generally involve the use of a catalyst composition formed from a compound of palladium, cobalt or nickel, a strong non-hydrohalogenic acid and a bidentate ligand of phosphorus, arsenic, antimony or nitrogen. The scope of the polymerization process is extensive but, without wishing to be limited, a preferred catalyst composition is formed from a compound of palladium, a non-hydrohalogenic acid having a pKa below 2 and a bidentate ligand of phosphorus.
The polymerization process whereby the linear alternating polymers are produced will typically provide a polymeric product which is substantially insoluble in the media of its production. In this as in many if not most polymerization processes producing insoluble product, some degree of reactor fouling takes place. This problem is reduced by the conventional procedures such as polishing the internal surfaces of the reactor or coating the surfaces with materials such as Teflon.RTM.. In copending U.S. patent application Ser. No. 338,246, filed Apr. 14, 1989, now U.S. Pat. No. 4,940,776 the degree of reactor fouling is reduced by incorporating in the reaction mixture a solid material including inorganic solids as well as preformed linear alternating polymer. It has also been proposed to add sulfonated polymeric solids to the reaction mixture as an acid component, e.g., U.S. patent application Ser. No. 908,899, filed Sept. 18, 1986, now U.S. Pat. No. 4,835,250 and other solids as a catalyst carrier for gas phase polymerization in U.S. patent application Ser. No. 053,780, filed May 26, 1987, now U.S. Pat. No. 4,778,876. It would be of advantage, however, to provide a polymerization process of producing linear alternating polymers whereby the extent of reactor fouling is reduced beyond that which would result from the mere presence of solid material in the polymerization mixture.